JP2015010113A - Moisture-proof insulation coating, sealing insulating treatment method using the coating, and electronic component - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photocurable moisture-proof insulation coating that has a low environmental load, has excellent depth curability and surface curability at a low irradiance, and moreover, has hydrophobicity and high long-term insulation reliability.SOLUTION: A moisture-proof insulation coating comprises a (meth) acryloyl group-containing compound (1), a photopolymerization initiator (2), and a mercapto group-containing compound (3).

Description

  The present invention relates to a moisture-proof insulating paint, a sealing / insulating method using the moisture-proof insulating paint, and an electronic component sealed and insulated with the moisture-proof insulating paint.

  Electronic and electrical devices tend to be smaller and lighter and more multifunctional year by year, and the mounting circuit boards mounted on various electronic and electrical devices that control them are insulated for the purpose of protecting them from moisture, dust, and gas. Has been done. In this insulation treatment method, a protective coating treatment with a paint such as an acrylic resin or a urethane resin is widely adopted. A paint for the purpose of moisture prevention and insulation treatment of a mounted circuit board mounted on an electronic / electrical device is referred to as a moisture-proof insulating paint. In addition, many resin compositions that can be cured by irradiation with ultraviolet rays or electron beams have been developed, and various photo-curable coatings have already been put into practical use and used for insulation treatment of mounted circuit boards. As such a resin composition, a modified acrylate resin composition derived from a polyester polyol compound or a polyolefin polyol compound is known.

  On the other hand, there is an increasing demand for ultraviolet irradiation devices using LED-UV lamps as UV lamps. An ultraviolet irradiation device using an LED-UV lamp has low power consumption and little generation of ozone. Therefore, there is an advantage that the running cost and the influence on the natural environment can be reduced. However, since the LED-UV lamp has a single wavelength unlike other UV lamps, the resin composition to be cured is required to have high sensitivity to ultraviolet rays. In particular, the surface that is in contact with air is exposed to inhibition of radical chain reaction by oxygen, and thus is liable to cause curing failure. When an LED-UV lamp is used, the solution is more difficult. Further, for further cost reduction, it is also required to cure the ends of the laminated electronic components at a time with a smaller exposure amount. Since the laminated ends are sealed at a time, if the resin film thickness is large and the exposure dose is small, curing failure due to the difficulty of reaching ultraviolet rays at the interface between the resin and the electronic component base material tends to occur. Also in this respect, high ultraviolet sensitivity is required. However, many photopolymerization initiators with high ultraviolet sensitivity deteriorate the electrical insulation, and there is a problem that they are not suitable for a resin composition used for insulation treatment.

  In response to the technical demands from the market as described above, Patent Document 1 discloses that a polyolefin polyol compound, an ethylenically unsaturated compound having a hydroxyl group, and a compound having two or more isocyanato groups in one molecule are reacted. A urethane compound having an ethylenically unsaturated double bond, a photopolymerizable monomer having 5 to 10 ethylenically unsaturated double bonds in the molecule, and a photopolymerization initiator. A photocurable resin composition is disclosed. However, although the compositions described in Examples of Patent Document 1 are cured with a small exposure amount, there is a problem that curing failure tends to occur at the resin / electronic component base material interface as the film thickness increases. On the other hand, although there is no description about poor surface hardening, there is a description of a photosensitizer that contributes to surface hardening. However, when a photosensitizer is used, the surface curability is improved, but the deep curability is deteriorated.

JP 2008-280414 A

  The present invention has been made in view of the above-described problems of the prior art, has a low environmental burden, is excellent in deep-part curability and surface curability at a low dose, and is hydrophobic and has high long-term insulation reliability. An object is to provide a photocurable moisture-proof insulating coating.

  Another object of the present invention is to provide a sealing insulation treatment method by curing a photocurable moisture-proof insulating paint for a mounting circuit board with an LED-UV lamp.

  It is another object of the present invention to provide a highly reliable electronic component that is sealed or insulated with the photocurable moisture-proof insulating paint for the mounting circuit board.

  As a result of repeated studies to solve the above problems, the present inventors have found that a photocurable moisture-proof insulating coating containing a (meth) acryloyl group-containing compound, a photopolymerization initiator, and a mercapto group-containing compound has a low environmental impact. The inventors have found that they have excellent deep-part curability and surface curability at a low irradiation dose, and are hydrophobic and have high long-term insulation reliability, thereby completing the present invention.

（式中、Ｒ^１はヘテロ原子を含んでいてもよい炭化水素基であり、Ｒ^２およびＲ^３は炭化水素基である。）
で表される化合物および／またはベンジルジメチルケタールであることを特徴とする［１］に記載の防湿絶縁塗料。
［３］メルカプト基含有化合物（３）が、１分子当たり２つ以上のメルカプト基を有することを特徴とする［１］または［２］に記載の防湿絶縁塗料。
［４］メルカプト基含有化合物（３）が、２級のメルカプト基を有することを特徴とする［１］〜［３］のいずれか１つに記載の防湿絶縁塗料。
［５］（メタ）アクリロイル基含有化合物（１）が、ポリオールポリ（メタ）アクリレート、エポキシ（メタ）アクリレート、ウレタン（メタ）アクリレートおよび（メタ）アクリルモノマーからなる群から選ばれる少なくとも１種を含む、［１］〜［４］のいずれか１つに記載の防湿絶縁塗料。
［６］（メタ）アクリロイル基含有化合物（１）が、ポリオールポリ（メタ）アクリレート、エポキシ（メタ）アクリレートおよび（メタ）アクリルモノマーからなる群から選ばれる少なくとも１種と、ウレタン（メタ）アクリレートとを含む、［１］〜［５］のいずれか１つに記載の防湿絶縁塗料。
［７］ウレタン（メタ）アクリレートが、水添ダイマー酸から誘導される構造単位および水添ダイマージオールから誘導される構造単位を有するポリエステルポリオールから誘導される構造を含むことを特徴とする［５］または［６］に記載の防湿絶縁塗料。
［８］さらに、シランカップリング剤（４）を含む［１］〜［７］のいずれか１つに記載の防湿絶縁塗料。
［９］さらに、粘着付与剤（５）を含む［１］〜［８］のいずれか１つに記載の防湿絶縁塗料。
［１０］［１］〜［９］のいずれか１つに記載の防湿絶縁塗料を電子部品に塗布し、塗布部にＬＥＤ−ＵＶランプを照射し、硬化させる工程を含む電子部品の封止絶縁処理方法。
［１１］［１］〜［９］のいずれか１つに記載の防湿絶縁塗料によって封止絶縁処理された電子部品。 That is, the present invention relates to the following [1] to [15].
[1] A moisture-proof insulating paint comprising a (meth) acryloyl group-containing compound (1), a photopolymerization initiator (2), and a mercapto group-containing compound (3).
[2] The photopolymerization initiator (2) is represented by the formula (1)

(In the formula, R ¹ is a hydrocarbon group which may contain a hetero atom, and R ² and R ³ are hydrocarbon groups.)
The moisture-proof insulating paint according to [1], which is a compound represented by the formula: and / or benzyldimethyl ketal.
[3] The moisture-proof insulating paint according to [1] or [2], wherein the mercapto group-containing compound (3) has two or more mercapto groups per molecule.
[4] The moisture-proof insulating paint according to any one of [1] to [3], wherein the mercapto group-containing compound (3) has a secondary mercapto group.
[5] The (meth) acryloyl group-containing compound (1) includes at least one selected from the group consisting of polyol poly (meth) acrylate, epoxy (meth) acrylate, urethane (meth) acrylate, and (meth) acrylic monomer. , [1] to [4].
[6] The (meth) acryloyl group-containing compound (1) is at least one selected from the group consisting of a polyol poly (meth) acrylate, an epoxy (meth) acrylate, and a (meth) acryl monomer, and a urethane (meth) acrylate, The moisture-proof insulating paint according to any one of [1] to [5].
[7] The urethane (meth) acrylate includes a structure derived from a polyester polyol having a structural unit derived from a hydrogenated dimer acid and a structural unit derived from a hydrogenated dimer diol. Or the moisture-proof insulating paint as described in [6].
[8] The moisture-proof insulating paint according to any one of [1] to [7], further including a silane coupling agent (4).
[9] The moisture-proof insulating paint according to any one of [1] to [8], further including a tackifier (5).
[10] Sealing insulation of an electronic component including a step of applying the moisture-proof insulating paint according to any one of [1] to [9] to an electronic component, irradiating the application portion with an LED-UV lamp and curing the coating portion Processing method.
[11] An electronic component that is sealed and insulated with the moisture-proof insulating paint according to any one of [1] to [9].

  The moisture-proof insulating paint of the present invention has low environmental impact, is excellent in deep-curing and surface-curing properties at a low dose, and is hydrophobic and has a long-term insulation reliability. The moisture-proof insulating paint is applied and cured. Thus, it is possible to produce an electronic component with high reliability.

  In addition, by applying the moisture-proof insulating paint of the present invention, irradiating the application portion with an LED-UV lamp and curing it, a highly reliable electronic component can be manufactured at low cost and with little environmental load.

Hereinafter, the present invention will be specifically described.
In the present specification, “(meth) acryloyl group” means an acryloyl group and / or a methacryloyl group.

<Dampproof insulating paint>
The moisture-proof insulating paint of the present invention contains a (meth) acryloyl group-containing compound (1), a photopolymerization initiator (2), and a mercapto group-containing compound (3).
First, the (meth) acryloyl group-containing compound (1) will be described.
If this component is a compound containing a (meth) acryloyl group, there will be no restriction | limiting in particular. However, the (meth) acryloyl group-containing compound (1) excludes those having a (meth) acryloyl group among the silane coupling agents (4) described later. That is, when the moisture-proof insulating paint of the present invention contains the silane coupling agent (4), when the silane coupling agent (4) contains a (meth) acryloyl group, the (meth) acryloyl group It is assumed that the silane coupling agent having a silane coupling agent is contained in the silane coupling agent (4) and not in the (meth) acryloyl group-containing compound (1).

  Examples of the (meth) acryloyl group-containing compound (1) include polyol poly (meth) acrylate, epoxy (meth) acrylate, urethane (meth) acrylate, and (meth) acrylic monomer.

  Polyol poly (meth) acrylate is an ester compound of polyol and acrylic acid or methacrylic acid. The polyol selected here is not particularly limited. For example, chain hydrogenated dimer diol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 1,5-pentanediol, Neopentyl glycol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 2-methyl-1,8-octanediol, 1,9-nonanediol, 2-ethyl-2-butyl-1, Chain aliphatic polyols such as 3-propanediol, 2,4-diethyl-1,5-pentanediol, 1,10-decanediol, 1,12-dodecanediol, polyolefin polyol, hydrogenated polyolefin polyol, and the like. Furthermore, hydrogenated dimer diol having an alicyclic structure, 1,4-cyclohexanedimethanol, 1,3-cyclohexane Examples include polyols having an alicyclic structure such as xanthodimethanol, tricyclo [5.2.1.02,6] decandimethanol, 2-methylcyclohexane-1,1-dimethanol, and further trimmertriol, p. -Polyols having an aromatic ring such as xylylene glycol, bisphenol A ethylene oxide adduct, bisphenol F ethylene oxide adduct, biphenol ethylene oxide adduct, etc., and further, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, etc. Polyether polyols, and polyester polyols such as polyhexamethylene adipate, polyhexamethylene succinate, polycaprolactone, and the like, and α, ω-poly (1,6-he Silene carbonate) diol, α, ω-poly (3-methyl-1,5-pentylene carbonate) diol, α, ω-poly [(1,6-hexylene: 3-methyl-pentamethylene) carbonate] diol, α , Ω-poly [(1,9-nonylene: 2-methyl-1,8-octylene) carbonate] diol, and the like, and further, structural units derived from hydrogenated dimer acid and A polyester polyol having a structural unit derived from a hydrogenated dimer diol can be mentioned. Of the above, examples of commercially available polyester polyols include trade names PLACEL, CD-205, 205PL, 205HL, 210, 210PL, 210HL, 220, 220PL, and 220HL, which are polycaprolactone polyols manufactured by Daicel Chemical Industries, Ltd. As an example of a commercially available product of (poly) carbonate diol, Kuraray Co., Ltd., α, ω-poly [(1,6-hexylene: 3-methyl-1,5-pentylene) carbonate] diol, trade name Kuraray polyol C-590, C-1065N, C-1015N, C-2015N, etc. are mentioned. These may be used alone or in combination of two or more. Moreover, the polyol which has an aromatic ring, polyether polyol, (poly) carbonate diol, and polyester polyol are mainly preferable from a viewpoint of the adhesiveness to a base material. More preferred is a polyester polyol having a structural unit derived from a hydrogenated dimer acid and a structural unit derived from a hydrogenated dimer diol.

  “Dimer acid” means a fatty acid having 14 to 22 carbon atoms having 2 to 4 ethylenic double bonds (hereinafter referred to as unsaturated fatty acid A), preferably 14 to 22 carbon atoms having two ethylenic double bonds. 22 fatty acids and fatty acids having 14 to 22 carbon atoms having 1 to 4 ethylenic double bonds (hereinafter referred to as unsaturated fatty acids B), preferably 14 to 14 carbon atoms having 1 or 2 ethylenic double bonds The dimer acid obtained by reacting 22 fatty acids with a double bond part shall be said. As the unsaturated fatty acid A, tetradecadienoic acid, hexadecadienoic acid, octadecadienoic acid (linoleic acid, etc.), eicosadienoic acid, docosadienoic acid, octadecatrienoic acid (linolenic acid, etc.), eicosatetraenoic acid ( Arachidonic acid and the like), and linoleic acid is most preferable. Moreover, as unsaturated fatty acid B, in addition to the above-mentioned examples, tetradecenoic acid (tuzuic acid, spermic acid, myristoleic acid) as a fatty acid having 14 to 22 carbon atoms having one ethylenic double bond , Hexadecenoic acid (such as palmitoleic acid), octadecenoic acid (such as oleic acid, elaidic acid, vaccenic acid), eicosenoic acid (such as gadoleic acid), docosenoic acid (such as erucic acid, cetreic acid, brassic acid), etc. Acid or linoleic acid is most preferred.

  In the dimerization reaction, the use ratio (molar ratio) of the unsaturated fatty acid A and the unsaturated fatty acid B is preferably about 1: 1.2 to 1.2: 1, and most preferably 1: 1. The dimerization reaction can be performed according to a known method, for example, a method described in JP-A-9-136861. That is, for example, an unsaturated fatty acid A and an unsaturated fatty acid B are mixed with a Lewis acid or Bronsted acid type liquid or solid catalyst, preferably montmorillonite activated clay, and the total amount of unsaturated fatty acid A and unsaturated fatty acid B is 100 parts by mass. It can be carried out by adding 1 to 20 parts by mass, preferably 2 to 8 parts by mass, and heating to 200 to 270 ° C., preferably 220 to 250 ° C. The pressure during the reaction is usually a slightly pressurized state, but may be normal pressure. The reaction time varies depending on the amount of catalyst and the reaction temperature, but is usually 5 to 7 hours. After completion of the reaction, the catalyst can be filtered off and then distilled under reduced pressure to distill off unreacted raw materials and isomerized fatty acids, and then dimer acid fraction can be distilled off. The dimerization reaction is thought to proceed through double bond transfer (isomerization) and Diels-Alder reaction, but the present invention is not limited thereto.

  The obtained dimer acid is usually a mixture of dimer acids having different structures depending on the bonding site or isomerization of the double bond, and may be used separately, but can be used as it is. Further, the obtained dimer acid contains a small amount of monomeric acid (for example, 6% by mass or less, particularly 4% by mass or less), trimer acid or higher polymer acid (for example, 6% by mass or less, particularly 4% by mass or less). May be.

  The “hydrogenated dimer acid” described in the present specification refers to a saturated dicarboxylic acid obtained by hydrogenating the carbon-carbon double bond of the dimer acid.

  When the dimer acid having 36 carbon atoms produced from, for example, linoleic acid and linoleic acid or oleic acid is used as the raw material, the structure of the main component of the hydrogenated dimer acid is represented by the following formula (4 ) And formula (5).

（式中、Ｒ^４およびＲ^５はアルキル基であり、かつＲ^４およびＲ^５に含まれる各炭素数、ａおよびｂの合計は２８（即ち、Ｒ^４に含まれる炭素数＋Ｒ^５に含まれる炭素数＋ａ＋ｂ＝２８）である。）

(In the formula, R ⁴ and R ⁵ are alkyl groups, and the number of carbon atoms contained in R ⁴ and R ⁵ , the sum of a and b is 28 (ie, the number of carbon atoms contained in R ⁴ + contained in R ⁵ ) Carbon number + a + b = 28).)

（式中、Ｒ^６およびＲ^７はアルキル基であり、かつＲ^６およびＲ^７に含まれる各炭素数、ｃおよびｄの合計は３２（即ち、Ｒ^６に含まれる炭素数＋Ｒ^７に含まれる炭素数＋ｃ＋ｄ＝３２）である。）

(In the formula, R ⁶ and R ⁷ are alkyl groups, and each carbon number contained in R ⁶ and R ⁷ , the sum of c and d is 32 (that is, the number of carbons contained in R ⁶ + contained in R ⁷ ) Carbon number + c + d = 32).)

  Examples of the commercially available hydrogenated dimer acid include PRIPOL (registered trademark) 1009 (manufactured by Croda), EMPOL (registered trademark) 1008, and EMPOL (registered trademark) 1062 (manufactured by BASF).

  The “hydrogenated dimer diol” described in the present specification refers to the reduction of at least one of the above dimer acid, the above hydrogenated dimer acid and the lower alcohol ester thereof in the presence of a catalyst, When the carboxylate moiety is alcohol and the raw material has a carbon-carbon double bond, the main component is a diol obtained by hydrogenating the double bond.

  For example, when a hydrogenated dimer diol is produced by reducing a hydrogenated dimer acid containing a compound having a structure represented by formula (4) or formula (5) as a main component, the main component of the hydrogenated dimer diol is reduced. The structure is a structure represented by the following formulas (6) and (7).

（式中、Ｒ^８およびＲ^９はアルキル基であり、かつＲ^８およびＲ^９に含まれる各炭素数、ｅおよびｆの合計は３０（即ち、Ｒ^８に含まれる炭素数＋Ｒ^９に含まれる炭素数＋ｅ＋ｆ＝３０）である。）

(In the formula, R ⁸ and R ⁹ are alkyl groups, and the total number of carbon atoms contained in R ⁸ and R ⁹ , and the sum of e and f is 30 (that is, contained in R ⁸ + R ^9. Carbon number + e + f = 30).)

（式中、Ｒ^１０およびＲ^１１はアルキル基であり、かつＲ^１０およびＲ^１１に含まれる各炭素数、ｇおよびｈの合計は３４（即ち、Ｒ^１０に含まれる炭素数＋Ｒ^１１に含まれる炭素数＋ｇ＋ｈ＝３４）である。）

(In the formula, R ¹⁰ and R ¹¹ are alkyl groups, and the total number of carbon atoms contained in R ¹⁰ and R ¹¹ , g and h is 34 (ie, the number of carbon atoms contained in R ¹⁰ + included in R ¹¹ ). Carbon number + g + h = 34).)

  Examples of the commercially available hydrogenated dimer diol include PRIPOL (registered trademark) 2033 and the like (manufactured by Croda) and Sovermol (registered trademark) 908 (manufactured by BASF).

  A polyester polyol having a structural unit derived from a hydrogenated dimer acid and a structural unit derived from a hydrogenated dimer diol, an acid component containing the hydrogenated dimer acid as an essential component and the hydrogenated dimer diol as essential The polyol component as a component can be produced by performing a condensation reaction in the presence of an esterification catalyst.

  Since the esterification reaction removes water, the reaction is generally performed at a reaction temperature of about 150 to 250 ° C. In general, the reaction is performed under normal pressure or reduced pressure.

  A polyester polyol having a structural unit derived from a hydrogenated dimer acid and a structural unit derived from a hydrogenated dimer diol includes a lower alkyl ester of an acid containing a hydrogenated dimer acid as an essential component, and the hydrogenated dimer described above. A polyol component containing diol as an essential component can also be produced by performing a transesterification reaction in the presence of a transesterification catalyst.

  Since the transesterification reaction removes alcohol, the reaction is generally performed at a reaction temperature of about 120 to 230 ° C. In general, the reaction is performed under normal pressure or reduced pressure.

  The amount of the polyol poly (meth) acrylate used in the moisture-proof insulating coating of the present invention is preferably 20 to 70% by mass, more preferably 24 to 60% by mass, based on the total polymerizable component. Especially preferably, it is 24-55 mass%. If the amount of the polyol poly (meth) acrylate used is less than 20% by mass relative to the total polymerizable component, the moisture-proof performance of the moisture-proof insulating coating may be lowered, which is not preferable. Moreover, when the usage-amount of polyol poly (meth) acrylate becomes more than 70 mass% with respect to all the polymeric components, the viscosity of a moisture-proof insulating coating will become high and handling may become difficult.

  Epoxy (meth) acrylate is a compound obtained by adding acrylic acid or methacrylic acid to the terminal epoxy group of an epoxy resin. There is no restriction | limiting in particular in the epoxy resin selected in this case. Specifically, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, novolac type epoxy resin, glycidyl ester type epoxy resin, biphenyl type epoxy resin and the like can be mentioned. These may be used alone or in combination of two or more.

  Examples of commercially available products of epoxy (meth) acrylate include epoxy ester 3000A (manufactured by Kyoeisha Chemical Co., Ltd.), EBECRYL600 (manufactured by Daicel-Cytec Co., Ltd.), EBECRYL6040 (manufactured by Daicel-Cytech Co., Ltd.), and the like.

  The amount of the epoxy (meth) acrylate used in the moisture-proof insulating coating of the present invention is preferably 20 to 70% by mass, more preferably 24 to 60% by mass, particularly with respect to the total polymerizable component. Preferably, it is 24-55 mass%. If the amount of the epoxy (meth) acrylate used is less than 20% by mass relative to the total polymerizable component, the moisture-proof performance of the moisture-proof insulating coating may be lowered, which is not preferable. Moreover, when the usage-amount of an epoxy (meth) acrylate becomes more than 70 mass% with respect to all the polymeric components, the viscosity of a moisture-proof insulating coating will become high and handling may become difficult.

  Urethane (meth) acrylate is a compound obtained by reacting polyol and polyisocyanate with hydroxyl group-containing (meth) acrylate, or polyol and isocyanato group-containing (meth) acrylate. There are no particular restrictions on the polyol, polyisocyanate, hydroxyl group-containing (meth) acrylate, and isocyanato group-containing (meth) acrylate selected at this time. The polyol is the same as the polyol used in the polyol poly (meth) acrylate. Examples of the polyisocyanate include 1,4-cyclohexane diisocyanate, isophorone diisocyanate, methylene bis (4-cyclohexyl isocyanate), 1,3-bis (isocyanatomethyl) cyclohexane, 1,4-bis (isocyanatomethyl) cyclohexane, , 4-tolylene diisocyanate, 2,6-tolylene diisocyanate, diphenylmethane-4,4'-diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, lysine triisocyanate, lysine diisocyanate, hexamethylene diisocyanate 2,4,4-trimethylhexamethylene diisocyanate, 2,2,4-trimethylhexanemethylene diisocyanate, norbornane diisocyanate, etc. And the like. These may be used alone or in combination of two or more. Examples of the hydroxyl group-containing (meth) acrylate include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, 4-hydroxybutyl acrylate, and 2-hydroxy-3-phenoxypropyl acrylate. 2-hydroxy-3- (o-phenylphenoxy) propyl acrylate, 2-hydroxyethyl acrylamide, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, 4-hydroxybutyl Methacrylate, 2-hydroxy-3-phenoxypropyl methacrylate, 2-hydroxy-3- (o-phenylphenoxy) pro Methacrylate, and the like. These may be used alone or in combination of two or more. Examples of the isocyanato group-containing (meth) acrylate include 2-isocyanatoethyl acrylate and 2-isocyanatoethyl methacrylate. These may be used alone or in combination of two or more.

  In the method for producing urethane (meth) acrylate, polyol and polyisocyanate and hydroxyl group-containing (meth) acrylate, or polyol and isocyanato in the presence or absence of a known urethanization catalyst such as dibutyltin dilaurate and dioctyltin dilaurate. Although the synthesis can be performed by reacting the group-containing (meth) acrylate, the reaction in the presence of a catalyst is preferable in terms of shortening the reaction time. However, if too much is used, there is a possibility that the physical properties at the time of actual use as a cured film will be adversely affected, so the amount used is polyol, polyisocyanate, hydroxyl group-containing (meth) acrylate, or polyol. It is preferable that it is 0.001-1 mass part with respect to 100 mass parts of total amounts of isocyanato group containing (meth) acrylate.

  Moreover, the said urethanization catalyst catalyzes the hydrolysis reaction of an alkoxy silyl group, when the moisture-proof insulating coating material of this invention contains an alkoxy silyl group. In such a case, it is necessary to consider the balance between the stability over time of the moisture-proof insulating paint of the present invention and the adhesion to the substrate, and the amounts used are polyol, polyisocyanate, and hydroxyl group-containing (meth) acrylate. Or 0.003 to 0.2 parts by mass, more preferably 0.005 to 0.15 parts by mass with respect to 100 parts by mass of the total amount of polyol and isocyanato group-containing (meth) acrylate. . When the amount is less than 0.001 part by mass, the effect of adding the catalyst is hardly exhibited, and when the amount is more than 1 part by mass, the physical property value in actual use as a cured film is finally affected as described above. There is.

  There are no particular restrictions on the order in which the raw materials are charged. Usually, in the case of a reaction of a polyol, a polyisocyanate, and a hydroxyl group-containing (meth) acrylate, the polyisocyanate and, if necessary, a urethanization catalyst are charged into the reactor. Stirring is performed, and then the polyol is charged at a temperature in the reactor of 50 ° C. to 140 ° C., preferably 60 ° C. to 120 ° C., and then the temperature in the reactor is 50 ° C. to 160 ° C., preferably 60 ° C. These are reacted at ~ 140 ° C. Thereafter, the temperature in the reactor is 30 ° C. to 120 ° C., preferably 50 ° C. to 100 ° C., a polymerization inhibitor and, if necessary, a urethanization catalyst are added, and a hydroxyl group-containing (meth) acrylate is added dropwise. During the dropping, the temperature in the reactor is preferably maintained at 30 to 120 ° C, desirably 50 to 100 ° C. After completion of the dropping, the temperature in the reactor is maintained at 30 to 120 ° C., preferably 50 to 100 ° C., to complete the reaction. In the case of a polyol and an isocyanato group-containing (meth) acrylate, the isocyanato group-containing (meth) acrylate, a polymerization inhibitor and, if necessary, a urethanization catalyst are charged into the reactor, followed by stirring, and then the temperature in the reactor The polyol is charged at 50 ° C. to 140 ° C., preferably 60 ° C. to 120 ° C., and then these are reacted at a temperature in the reactor of 50 ° C. to 160 ° C., preferably 60 ° C. to 140 ° C. Thereafter, the temperature in the reactor is maintained at 30 ° C. to 120 ° C., desirably 50 ° C. to 100 ° C., to complete the reaction.

  In the case of a reaction between a polyol, a polyisocyanate, and a hydroxyl group-containing (meth) acrylate, the raw material charge molar ratio (ie, (number of hydroxyl groups in the polyol) / (number of isocyanate groups in the polyisocyanate) / (hydroxyl group-containing (meta)) ) The number of hydroxyl groups in the acrylate)) is adjusted according to the molecular weight of the target polyurethane. However, it is preferable to increase the number of isocyanato groups in the polyisocyanate than the number of hydroxyl groups in the polyol.

  When the ratio of the total number of hydroxyl groups in the polyol to the number of isocyanate groups in the polyisocyanate is close to 1.0, the molecular weight increases. When the ratio deviates from 1.0, the molecular weight decreases.

  The feed molar ratio of the raw material is not particularly limited, but the ratio of the number of isocyanate groups in the polyisocyanate and the total number of hydroxyl groups in the polyol is preferably in the range of 4: 1 to 1.5: 1.

  If this ratio is larger than 4: 1, the abundance of structural units derived from polyol may be reduced, which may be undesirable in terms of moisture resistance of the moisture-proof insulating coating. Moreover, when it is smaller than 1.4: 1, the molecular weight becomes too large, and when used in the moisture-proof insulating paint of the present invention, the viscosity may become too high.

  The amount of the urethane (meth) acrylate used in the moisture-proof insulating coating of the present invention is preferably 20 to 70% by mass, more preferably 24 to 60% by mass, particularly with respect to the total polymerizable component. Preferably, it is 24-55 mass%. If the amount of urethane (meth) acrylate used is less than 20% by mass relative to the total polymerizable component, the moisture-proof performance of the moisture-proof insulating coating may be lowered, which is not preferable. Moreover, when the usage-amount of urethane (meth) acrylate becomes more than 70 mass% with respect to all the polymeric components, the viscosity of a moisture-proof insulating coating material will become high and handling may become difficult.

  Among urethane (meth) acrylates, urethane (meth) acrylate derived from a polyester polyol having a structural unit derived from a hydrogenated dimer acid and a structural unit derived from a hydrogenated dimer diol is particularly preferable.

  The (meth) acrylic monomer in this specification is a compound obtained by removing the polyol poly (meth) acrylate, the epoxy (meth) acrylate, and the urethane (meth) acrylate from the (meth) acryloyl group-containing compound.

  Examples of (meth) acrylic monomers include (meth) acryloyl-containing compounds having a cyclic ether group such as glycidyl acrylate, tetrahydrofurfuryl acrylate, glycidyl methacrylate, and tetrahydrofurfuryl methacrylate, cyclohexyl acrylate, isobornyl acrylate, and dicyclopentenyl. Acrylate, dicyclopentenyloxyethyl acrylate, dicyclopentanyl acrylate, dicyclopentanyl ethyl acrylate, 4-tert-butylcyclohexyl acrylate, cyclohexyl methacrylate, isobornyl methacrylate, dicyclopentenyl methacrylate, dicyclopentenyloxyethyl methacrylate, Dicyclopentanyl methacrylate, dicyclopentanylethyl Monofunctional (meth) acryloyl group-containing compounds having a cyclic aliphatic group such as tacrylate, 4-tert-butylcyclohexyl methacrylate, lauryl acrylate, isononyl acrylate, 2-ethylhexyl acrylate, isobutyl acrylate, tert-butyl acrylate, isooctyl acrylate Monofunctional (meth) acryloyl group-containing compounds having a chain aliphatic group such as isoamyl acrylate, lauryl methacrylate, isononyl methacrylate, 2-ethylhexyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, isooctyl methacrylate, isoamyl methacrylate, benzyl Acrylate, phenoxyethyl acrylate, benzyl methacrylate, phenoxyethyl methacrylate Monofunctional (meth) acryloyl group-containing compound having an aromatic ring such as 2-hydroxy-3-phenoxypropyl methacrylate, polyethylene glycol diacrylate, decanediol diacrylate, nonanediol diacrylate, hexanediol diacrylate, tricyclode Mention may be made of polyfunctional (meth) acryloyl group-containing compounds such as candimethanol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate and the like.

  The amount of the (meth) acrylic monomer used in the moisture-proof insulating coating of the present invention is preferably 30 to 80% by mass, more preferably 40 to 70% by mass, and still more preferably based on the total polymerizable component. Is 45-70 mass%. If the amount of the (meth) acrylic monomer used is more than 80% by mass relative to the total polymerizable component, the moisture-proof performance of the moisture-proof insulating paint may be lowered, which is not preferable. Moreover, when the usage-amount of a (meth) acryl monomer will be less than 30 mass% with respect to all the polymeric components, the viscosity of a moisture-proof insulation coating material may become high, and handling may become difficult.

  The “polymerizable component” described in the present specification means a compound that can be polymerized by radical polymerization, and the “total polymerizable component” means the total amount of the polymerizable component. The (meth) acryloyl group-containing compound (1) is all contained in the polymerizable component. P-styryltrimethoxysilane, p-styryltriethoxysilane, 3-acryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-acryloyloxypropyltriethoxy in the silane coupling agent (4) described later Radicals of silane, 3-methacryloyloxypropyltriethoxysilane, 3-acryloyloxypropylmethyldimethoxysilane, 3-methacryloyloxypropylmethyldimethoxysilane, 3-acryloyloxypropylmethyldiethoxysilane, 3-methacryloyloxypropylmethyldiethoxysilane A silane coupling agent having a polymerizable unsaturated group is also included in the polymerizable component.

  Further, a (meth) acrylic monomer having a chain aliphatic hydrocarbon group having 9 or more carbon atoms such as lauryl acrylate, isononyl acrylate, lauryl methacrylate, isononyl methacrylate, etc. with respect to the total amount of (meth) acrylic monomer, Isobornyl acrylate, dicyclopentenyl acrylate, dicyclopentenyloxyethyl acrylate, dicyclopentanyl acrylate, dicyclopentanyl ethyl acrylate, 4-tert-butylcyclohexyl acrylate, isobornyl methacrylate, dicyclopentenyl methacrylate, dicyclo Pentenyloxyethyl methacrylate, dicyclopentanyl methacrylate, dicyclopentanyl ethyl methacrylate, 4-tert-butylcyclohexyl methacrylate Having a number of 9 or more cyclic aliphatic hydrocarbon group of carbon atoms of is preferably (meth) the total amount of the acrylic monomer is more than 50 mass%.

Next, the photopolymerization initiator (2) will be described.
The photopolymerization initiator is not particularly limited as long as it is a compound that generates radicals that contribute to the initiation of radical polymerization upon irradiation with light such as near infrared rays, visible rays, and ultraviolet rays.

  Specific examples of the photopolymerization initiator include acetophenone, 2,2-dimethoxy-2-phenylacetophenone, diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, 1,2-hydroxy-2-methyl-1-phenylpropane. -1-one, α-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropanone, 2-hydroxy-2-methyl-1- (4-isopropylphenyl) propanone, 2-hydroxy-2- Methyl-1- (4-dodecylphenyl) propanone and 2-hydroxy-2-methyl-1-[(2-hydroxyethoxy) phenyl] propanone, benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methyl Benzophenone, 4-methoxy Nzophenone, 2-chlorobenzophenone, 4-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone, 2-ethoxycarbonylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, benzophenone tetracarboxylic acid or tetramethyl ester thereof, 4 , 4'-bis (dialkylamino) benzophenones (for example, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (dicyclohexylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, 4, 4'-bis (dihydroxyethylamino) benzophenone), 4-methoxy-4'-dimethylaminobenzophenone, 4,4'-dimethoxybenzophenone, 4-dimethylaminobenzophenone, 4- Dimethylaminoacetophenone, benzyl, anthraquinone, 2-t-butylanthraquinone, 2-methylanthraquinone, phenanthraquinone, fluorenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone, 2 -(Dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone, 2-methyl-1- [4- (methylthio) phenyl]- 2-morpholino-1-propanone, 2-hydroxy-2-methyl- [4- (1-methylvinyl) phenyl] propanol oligomer, benzoin, benzoin ethers (for example, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin) Isopropyl ether, Zoin isobutyl ether, benzoin phenyl ether, benzyldimethyl ketal), acridone, chloroacridone, N-methylacridone, N-butylacridone, N-butyl-chloroacridone, 2,4,6-trimethylbenzoyldiphenylphosphine Oxide, 2,6-dimethoxybenzoyldiphenylphosphine oxide, 2,6-dichlorobenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylmethoxyphenylphosphine oxide, 2,4,6-trimethylbenzoylethoxyphenylphosphine oxide, 2, 3,5,6-tetramethylbenzoyldiphenylphosphine oxide, benzoyldi- (2,6-dimethylphenyl) phosphonate, 1- [4- (phenylthio) phene L] -1,2-octanedione-2- (O-benzoyloxime), 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone-1- (O— Acetyloxime), 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -3-cyclopentylpropanone-1- (O-acetyloxime), 1- [4- ( Phenylthio) phenyl] -3-cyclopentylpropane-1,2-dione-2- (O-benzoyloxime) and the like. Examples of bisacylphosphine oxides include bis- (2,6-dichlorobenzoyl) phenylphosphine oxide, bis- (2,6-dichlorobenzoyl) -2,5-dimethylphenylphosphine oxide, bis- (2, 6-dichlorobenzoyl) -4-propylphenylphosphine oxide, bis- (2,6-dichlorobenzoyl) -1-naphthylphosphine oxide, bis- (2,6-dimethoxybenzoyl) phenylphosphine oxide, bis- ( 2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, bis- (2,6-dimethoxybenzoyl) -2,5-dimethylphenylphosphine oxide, bis- (2,4,6- Trimethylbenzoyl) phenyl phosphite Oxide, (2,5,6-trimethylbenzoyl) -2,4,4-trimethylpentylphosphine oxide, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1 -Chloro-4-propoxythioxanthone and the like.

  Moreover, a metallocene compound can also be used as a photopolymerization initiator. As the metallocene compound, the transition metal represented by Fe, Ti, V, Cr, Mn, Co, Ni, Mo, Ru, Rh, Lu, Ta, W, Os, Ir, etc. can be used as the metallocene compound, An example is bis (η5-2,4-cyclopentadien-1-yl) -bis [2,6-difluoro-3- (pyrrol-1-yl) phenyl] titanium.

  These photopolymerization initiators can be used alone or in combination of two or more.

  More preferred as the photopolymerization initiator used in the present invention is a compound represented by the following formula (1) or benzyldimethyl ketal.

式中、Ｒ^１、Ｒ^２、Ｒ^３は特に構造を限定されないが、Ｒ^１はヘテロ原子を含んでいてもよい炭化水素基であり、Ｒ^２およびＲ^３は炭化水素基である。好ましくは、Ｒ^１はヘテロ原子を含む構造であり、Ｒ^２およびＲ^３はアルキル基、および／またはフェニル基、および／またはシクロアルキル基を含む構造である。より好ましくは、Ｒ^１は式（２）または式（３）で表され、Ｒ^２は炭素数１〜１０の炭化水素基であり、Ｒ^３はメチル基またはフェニル基である。さらに好ましくは、Ｒ^２は炭素数１〜６のアルキル基である。

In the formula, R ¹ , R ² and R ³ are not particularly limited in structure, but R ¹ is a hydrocarbon group which may contain a hetero atom, and R ² and R ³ are hydrocarbon groups. Preferably, R ¹ is a structure containing a hetero atom, and R ² and R ³ are structures containing an alkyl group, and / or a phenyl group, and / or a cycloalkyl group. More preferably, R ¹ is represented by formula (2) or formula (3), R ² is a hydrocarbon group having 1 to 10 carbon atoms, and R ³ is a methyl group or a phenyl group. More preferably, R ² is an alkyl group having 1 to 6 carbon atoms.

  Examples of the compound represented by the formula (1) include Irgacure OXE 01, Irgacure OXE 02 (both manufactured by BASF), TR-PBG-304, TR-PBG-305 (both Changzhou Strong Electronic New Materials Co., Ltd. ( CHANGZHOU TRONLY NEW ELECTRONIC MATERIALS CO., LTD), etc. In addition, examples of benzyldimethyl ketal include Irgacure 651 (manufactured by BASF), which may be used alone or in combination of two or more. Further, benzyl dimethyl ketal is most preferable from the viewpoint of storage stability when blended in a moisture-proof insulating coating.

  The amount of the compound represented by the formula (1) or the benzyl dimethyl ketal used is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 100 parts by mass of the total photopolymerizable component. It is the range of -6 mass parts. When the amount of the compound represented by the formula (1) or the benzyldimethyl ketal is less than 0.1 parts by mass with respect to 100 parts by mass of the total photopolymerizable component, the deep curability is hardly exhibited. Become. Moreover, when the usage-amount of the compound or benzyl dimethyl ketal represented by Formula (1) becomes more than 10 mass parts with respect to 100 mass parts of all the photopolymerizable components, there exists a possibility of affecting the physical property of hardened | cured material. is there.

  Preferred as a photocuring initiator represented by formula (1) or a photopolymerization initiator combined with benzyldimethyl ketal is 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone, 2- (Dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone. Examples of 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone include Irgacure 369 (manufactured by BASF). Further, as 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone, for example, Irgacure 379EG (manufactured by BASF) and the like Is mentioned.

  The amount of the photopolymerization initiator other than the compound represented by the formula (1) or benzyldimethyl ketal is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the total photopolymerizable component. Preferably, it is the range of 0.5-6 mass parts. These photopolymerization initiators other than the compound represented by the formula (1) or benzyl dimethyl ketal may be used alone or in combination of two or more. When the amount of the compound represented by the formula (1) or the benzyldimethyl ketal is less than 0.1 parts by mass with respect to 100 parts by mass of the total photopolymerizable component, the photopolymerization initiation performance is hardly exhibited. . Moreover, when the usage-amount of photoinitiators other than the compound represented by Formula (1) or benzyl dimethyl ketal exceeds 10 mass parts with respect to 100 mass parts of all photopolymerizable components, it will become the physical property of hardened | cured material. May have an impact.

Next, the mercapto group-containing compound (3) will be described.
The mercapto group-containing compound (3) is not particularly limited as long as it is a compound containing a mercapto group.

  Specific examples of the mercapto group-containing compound include n-dodecyl mercaptan, n-octyl mercaptan, n-butyl mercaptan, tert-butyl mercaptan, n-lauryl mercaptan, mercaptoethanol, mercaptopropanol, triethylene glycol dimercaptan, 1 , 4-bis (3-mercaptobutyryloxy) butane, trimethylolethanetris (3-mercaptobutyrate), trimethylolpropane tris (3-mercaptobutyrate), 1,3,5-tris (3-mercaptobutyrate) Ryloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, pentaerythritol tetrakis (3-mercaptobutyrate) and the like. Among them, preferred are triethylene glycol dimercaptan, 1,4-bis (3-mercaptobutyryloxy) butane, trimethylolethane tris (3-mercaptobutyrate), trimethylolpropane tris (bifunctional or higher). 3-mercaptobutyrate), 1,3,5-tris (3-mercaptobutyryloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, pentaerythritol tetrakis ( 3-mercaptobutyrate) and the like. More preferably, 1,4-bis (3-mercaptobutyryloxy) butane having a secondary mercapto group, trimethylolethane tris (3-mercaptobutyrate), trimethylolpropane tris (3-mercaptobutyrate), 1,3,5-tris (3-mercaptobutyryloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, pentaerythritol tetrakis (3-mercaptobutyrate) is there.

  The amount of the mercapto group-containing compound (3) used is preferably 1 to 20 parts by mass, more preferably 2 to 10 parts by mass with respect to 100 parts by mass of the total photopolymerizable component. When the usage-amount of a mercapto group containing compound (3) is less than 1 mass part with respect to 100 mass parts of all photopolymerizable components, surface curability will become difficult to be expressed. If the amount of the rucapto group-containing compound (3) used is more than 20 parts by mass with respect to 100 parts by mass of the total photopolymerizable component, the physical properties of the cured product may be affected, and the storage stability deteriorates. There is also a possibility to do.

  A method for measuring the thickness of the cured film obtained by curing the moisture-proof insulating paint of the present invention will be described. The thickness of the cured film is measured using an outer micrometer. At this time, it is preferable to use an outer micrometer having a constant pressure mechanism in order to reduce measurement errors for each measurement trial and each measurer. Examples of the constant pressure mechanism include a ratchet stop type.

  In the moisture-proof insulating coating of the present invention, a polymerization inhibitor may be added in order to increase storage stability and is preferable.

The polymerization inhibitor is not particularly limited. For example, hydroquinone, p-methoxyphenol, p-benzoquinone, naphthoquinone, phenanthraquinone, tolquinone, 2,5-diacetoxy-p-benzoquinone, 2,5-dicaproxy-p-benzoquinone, 2,5-acyloxy-p-benzoquinone, 2,5-di-tert-butyl-3-methylphenol, pt-butylcatechol, 2,5-di-t- Butyl hydroquinone, p-tert-butyl catechol, mono-t-butyl hydroquinone, 2,5-di-t-amyl hydroquinone, di-t-butyl paracresol hydroquinone monomethyl ether, alpha naphthol, acetamidine acetate, acetamidine sulfate , Phenylhydrazine hydrochloride, hydride Gin hydrochloride, trimethylbenzylammonium chloride, laurylpyridinium chloride, cetyltrimethylammonium chloride, phenyltrimethylammonium chloride, trimethylbenzylammonium oxalate, di (trimethylbenzylammonium) oxalate, trimethylbenzylammonium malate, trimethylbenzylammonium tartrate, Trimethylbenzylammonium glycolate, phenyl-β-naphthylamine, parabenzylaminophenol, di-β-naphthylparaphenylenediamine, dinitrobenzene, trinitrotoluene, picric acid, cyclohexanone oxime, pyrogallol, tannic acid, resorcin, triethylamine hydrochloride, dimethyl Aniline hydrochloride and dibutyla Down the hydrochloride salt, and the like.
These may be used alone or in combination of two or more.

  Among these, hydroquinone, p-methoxyphenol, p-benzoquinone, naphthoquinone, phenanthraquinone, tolquinone, 2,5-diacetoxy-p-benzoquinone, 2,5-dicaproxy-p-benzoquinone, 2,5-acyloxy- p-benzoquinone, p-t-butylcatechol, 2,5-di-t-butylhydroquinone, p-tert-butylcatechol, mono-t-butylhydroquinone, 2,5-di-t-amylhydroquinone, di-t -Butyl paracresol hydroquinone monomethyl ether and phenothiazine are preferably used.

Usually, it is preferable to add 0.01-10 mass parts of this polymerization inhibitor with respect to 100 mass parts of all the polymerizable components.
The moisture-proof insulating paint of the present invention can further contain a silane coupling agent (4) for the purpose of imparting adhesion to glass, metal or metal oxide.

The silane coupling agent (4) is an organosilicon compound having both a functional group reactively bonded to an organic material and a functional group reactively bonded to an inorganic material in the molecule, and the structure is generally represented by the following formula (8). Shown in

Here, Y is a functional group reactively bonded to an organic material, and representative examples thereof include a vinyl group, an epoxy group, an amino group, a substituted amino group, a (meth) acryloyl group, a mercapto group and the like. X is a functional group that reacts with an inorganic material and is hydrolyzed by water or moisture to produce silanol. This silanol reacts with the inorganic material. Representative examples of X include an alkoxy group, an acetoxy group, a chloro atom, and the like. R ¹² is a divalent organic group, and R ¹³ represents an alkyl group. i represents an integer of 1 to 3, and j represents an integer of 0 to 2. However, i + j = 3.

  Examples of the silane coupling agent include 3-isocyanatopropyltriethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropylmethyldiethoxysilane, 3-isocyanatopropylmethyldimethoxysilane, p-styryltrimethoxysilane, p -Styryltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriisopropoxysilane, vinyltris (2-methoxyethoxy) silane, 3-acryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3 -Acryloyloxypropyltriethoxysilane, 3-methacryloyloxypropyltriethoxysilane, 3-acryloyloxypropylmethyldimethyl Xysilane, 3-methacryloyloxypropylmethyldimethoxysilane, 3-acryloyloxypropylmethyldiethoxysilane, 3-methacryloyloxypropylmethyldiethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycid Xylpropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, N-2- (aminoethyl) -3-aminopropyl Methyldimethoxysilane, N- (2-minoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-a Nopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyl Examples include triethoxysilane and allyltrimethoxysilane.

  Among these, Y is preferably a compound having reactivity with (meth) acryloyl group-containing compound (1) and urethane (meth) acrylate, and among them, p-styryltrimethoxysilane, p-styryl. Triethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriisopropoxysilane, vinyltris (2-methoxyethoxy) silane, 3-acryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-acryloyl Oxypropyltriethoxysilane, 3-methacryloyloxypropyltriethoxysilane, 3-acryloyloxypropylmethyldimethoxysilane, 3-methacryloyloxypropylmethyldimethoxysilane, 3-acrylic Iloxypropylmethyldiethoxysilane and 3-methacryloyloxypropylmethyldiethoxysilane are preferred, and more preferably 3-acryloyloxypropyltrimethoxysilane and 3-methacryloyl which are easily incorporated into the cured product during the photocuring reaction. Oxypropyltrimethoxysilane, 3-acryloyloxypropyltriethoxysilane, 3-methacryloyloxypropyltriethoxysilane, 3-acryloyloxypropylmethyldimethoxysilane, 3-methacryloyloxypropylmethyldimethoxysilane, 3-acryloyloxypropylmethyldiethoxy Silane, 3-methacryloyloxypropylmethyldiethoxysilane, especially considering the reactivity of the alkoxysilyl group, Shi propyltrimethoxysilane, 3-methacryloyloxy propyl trimethoxy silane, 3-acryloyloxypropyl methyl dimethoxysilane, 3-methacryloyloxypropyl methyl dimethoxysilane is preferable.

  The silane coupling agent (4) is preferably in the range of 0.01 to 8 parts by mass with respect to 100 parts by mass of all polymerizable components in the moisture-proof insulating coating of the present invention, more preferably, It is the range of 1 mass part-5 mass parts. In the case of less than 0.01 part by mass with respect to 100 parts by mass of all polymerizable components in the moisture-proof insulating paint of the present invention (I), adhesion to glass, metal or metal oxide may not be sufficiently exhibited. is there. Moreover, when it is more than 8 mass% with respect to 100 mass parts of all the polymeric components in the moisture-proof insulating coating material of this invention, there exists a tendency for the surface tack of hardened | cured material to increase depending on the kind of silane coupling agent to be used. .

  The moisture-proof insulating paint of the present invention can further contain a tackifier (5) for the purpose of imparting adhesion to the substrate.

  The tackifier used in the moisture-proof insulating paint of the present invention is a substance for providing an adhesive function by blending with urethane (meth) acrylate or a polymer compound typified by elastomer having rubber elasticity, and A compound having a molecular weight of several hundred to several thousand and having a property of not exhibiting rubber elasticity by itself in a glass state at room temperature is preferable.

  Examples of the tackifier include petroleum resin tackifiers, terpene resin tackifiers, rosin resin tackifiers, coumarone indene resin tackifiers, and styrene resin tackifiers.

  Examples of petroleum resin tackifiers include aliphatic petroleum resins, aromatic petroleum resins, aliphatic-aromatic copolymer petroleum resins, alicyclic petroleum resins, dicyclopentadiene resins, and hydrogenated products thereof. Of the modified product. The petroleum resin may be C5-based or C9-based.

  Examples of the terpene resin tackifier include β-pinene resin, α-pinene resin, terpene-phenol resin, aromatic modified terpene resin, hydrogenated terpene resin and the like. These terpene resins are preferably resins having no polar group.

Rosin resin tackifiers include rosins such as gum rosin, tall oil rosin, wood rosin; hydrogenated rosin, disproportionated rosin, polymerized rosin, modified rosin such as maleated rosin; rosin glycerin ester, hydrogenated rosin ester, water Examples thereof include rosin esters such as rosin glycerol ester. These rosin resins have polar groups.
These tackifiers can be used alone or in combination of two or more.

  These tackifiers preferably contain a petroleum resin tackifier or a terpene resin tackifier, and more preferably contain a petroleum resin tackifier.

  It is desirable that the total amount of tackifier is 0.1 to 35 parts by mass with respect to 100 parts by mass of all polymerizable components. When the total amount of the tackifier is less than 0.1 parts by mass with respect to 100 parts by mass of the total polymerizable component, it is not preferable that the effect of adding the tackifier is hardly expressed. Moreover, when the total amount of tackifier is more than 35 parts by mass with respect to 100 parts by mass of all polymerizable components, the moisture-proof insulating paint of the present invention may become cloudy or the viscosity may become too high.

  Moreover, a radical chain transfer agent can be used for the moisture-proof insulating paint of this invention as needed.

  As the radical chain transfer agent, a compound that has the function of reactivating the polymerization active species trapped by an inert radical scavenger such as oxygen and contributes to the improvement of the surface curability can be used. Examples of the compound serving as a chain transfer agent include N, N-dimethylaniline, N, N-dimethyl-p-toluidine, N, N-dimethyl-m-toluidine, N, N-diethyl-p-toluidine, N, N. -Dimethyl-3,5-dimethylaniline, N, N-dimethyl-3,4-dimethylaniline, N, N-dimethyl-4-ethylaniline, N, N-dimethyl-4-isopropylaniline, N, N-dimethyl -4-t-butylaniline, N, N-dimethyl-3,5-di-t-butylaniline, N, N-bis (2-hydroxyethyl) -3,5-dimethylaniline, N, N-di ( 2-hydroxyethyl) -p-toluidine, N, N-bis (2-hydroxyethyl) -3,4-dimethylaniline, N, N-bis (2-hydroxyethyl) -4-ethylaniline, , N-bis (2-hydroxyethyl) -4-isopropylaniline, N, N-bis (2-hydroxyethyl) -4-t-butylaniline, N, N-bis (2-hydroxyethyl) -3,5 -Di-isopropylaniline, N, N-bis (2-hydroxyethyl) -3,5-di-t-butylaniline, 4-N, N-dimethylaminobenzoic acid ethyl ester, 4-N, N-dimethylamino Benzoic acid methyl ester, N, N-dimethylaminobenzoic acid n-butoxyethyl ester, 4-N, N-dimethylaminobenzoic acid 2- (methacryloyloxy) ethyl ester, 4-N, N-dimethylaminobenzophenone, trimethylamine, Triethylamine, N-methyldiethanolamine, N-ethyldiethanolamine, Nn-butyldiethanol Amine, N-lauryl diethanolamine, triethanolamine, 2-ethylhexyl-4-dimethylaminobenzoate, 2- (dimethylamino) ethyl methacrylate, N-methyldiethanolamine dimethacrylate, N-ethyldiethanolamine dimethacrylate, triethanolamine mono Methacrylate, triethanolamine dimethacrylate, triethanolamine trimethacrylate and the like can be mentioned. Particularly suitable amines are 2-ethylhexyl-4-dimethylaminobenzoate.

  In the moisture-proof insulating paint of the present invention, when a radical chain transfer agent is used, the amount used becomes high sensitivity when the amount is 0.01 to 10 parts by mass with respect to 100 parts by mass of all polymerizable components. Improves surface curability in air. More preferably, the surface curability is further improved within the range of 0.5 to 5 parts by mass. These radical chain transfer agents may be used alone or in combination of two or more.

  The moisture-proof insulating paint of the present invention preferably has a viscosity at 25 ° C. of 2000 mPa · s or less. More preferably, the viscosity at 25 ° C. is 1600 mPa · s or less. When the viscosity at 25 ° C. is higher than 2000 mPa · s, when the curable composition is applied by a drawing application method using a dispenser, the spread after application is suppressed, and as a result, the thickness after curing is more than necessary. May increase.

A method for measuring the viscosity of the moisture-proof insulating paint of the present invention will be described.
The viscosity is measured using a viscometer. Examples of the viscometer include a capillary tube viscometer, a falling ball viscometer, and a rotary viscometer. Of these, a rotary viscometer is preferably used.

  The typical conditions when performing viscosity measurement using a rotary viscometer will be described. Using a 1 mL sample, a rotary viscometer (manufactured by Brookfield, model: DV-II + Pro), a cone plate type spindle of model number CPE-42, temperature 25.0 ° C., rotation speed 10 rpm Measure the value when the viscosity becomes almost constant.

The moisture-proof insulating paint of the present invention can contain a filler, a modifier, an antifoaming agent, a colorant, and the like as necessary within a range that does not adversely affect fluidity and photocurability.
Examples of the filler include fine powder silicon oxide, magnesium oxide, aluminum hydroxide, calcium carbonate and the like.

  Examples of the modifier include a leveling agent for improving leveling properties. As the leveling agent, for example, polyether-modified dimethylpolysiloxane copolymer, polyester-modified dimethylpolysiloxane copolymer, polyether-modified methylalkylpolysiloxane copolymer, aralkyl-modified methylalkylpolysiloxane copolymer, etc. can be used. . These may be used alone or in combination of two or more. 0.01-10 mass parts can be added with respect to 100 mass parts of all the polymerizable components. When the amount is less than 0.01 part by mass, the effect of adding the leveling agent may not be exhibited. On the other hand, when the amount is more than 10 parts by mass, depending on the type of leveling agent used, there is a possibility of surface tack or deterioration of electrical insulation characteristics.

  The antifoaming agent is not particularly limited as long as it literally has an action of eliminating or suppressing bubbles generated or remaining when the moisture-proof insulating paint of the present invention is applied.

  Examples of the antifoaming agent used in the moisture-proof insulating coating of the present invention (I) include known antifoaming agents such as silicone oils, fluorine-containing compounds, polycarboxylic acid compounds, polybutadiene compounds, and acetylenic diol compounds. . Specific examples thereof include, for example, BYK-077 (manufactured by Big Chemie Japan Co., Ltd.), SN deformer 470 (manufactured by San Nopco Co., Ltd.), TSA750S (manufactured by Momentive Performance Materials LLC), silicone oil SH-203 (Toray Industries, Inc.) -Silicone defoaming agents such as Dow Corning Co., Ltd., Dappo SN-348 (San Nopco Co., Ltd.), Dappo SN-354 (San Nopco Co., Ltd.), Dappo SN-368 (San Nopco Co., Ltd.), Disparon 230HF Acetylene diol system such as acrylic polymer antifoaming agents (made by Enomoto Kasei Co., Ltd.), Surfynol DF-110D (made by Nissin Chemical Industry Co., Ltd.), Surfynol DF-37 (made by Nissin Chemical Industry Co., Ltd.) Defoaming agent, fluorine-containing silico such as FA-630 Emissions-based anti-foaming agents, and the like can be mentioned. These may be used alone or in combination of two or more. Usually, 0.001-5 mass parts can be added with respect to 100 mass parts of all the polymerizable components. If the amount is less than 0.01 parts by mass, the effect of adding the antifoaming agent may not be exhibited. On the other hand, when the amount is more than 5 parts by mass, depending on the type of antifoaming agent to be used, surface tack may occur or electrical insulation characteristics may be deteriorated.

  Examples of the colorant include known inorganic pigments, organic pigments, organic dyes, and the like, and each is blended according to a desired color tone. These may be used alone or in combination of two or more.

<Sealing insulation treatment method>
In the sealing insulation treatment method of the present invention, the moisture-proof insulating paint of the present invention is applied to an electronic component, and then the LED-UV lamp is irradiated to the moisture-proof insulating paint coating portion to be cured. The method for applying the moisture-proof insulating coating is not particularly limited, but examples include dipping, brushing, spraying, and drawing. The method of irradiating the moisture-proof insulating paint application part with ultraviolet rays from the LED-UV lamp is not particularly limited, but the electronic parts coated with the moisture-proof insulating paint by holding or operating the flexible light guide tube by hand or machine are irradiated. And a method of placing an electronic component coated with a moisture-proof insulating paint on a conveyor and irradiating it through an area irradiated with ultraviolet rays from an LED-UV lamp.

  A method for evaluating long-term insulation reliability when insulation treatment is performed by the sealing insulation treatment method of the present invention will be described. Long-term insulation reliability evaluation is performed, for example, under conditions of temperature and humidity exceeding the range of normal temperature and normal humidity defined in JIS Z 8703 “Standard condition of test place”, that is, temperature of 35 ° C. or higher and humidity of 85% RH or higher. The evaluation is performed by applying a bias voltage to the comb-shaped pattern substrate to which the moisture-proof insulating paint is applied and measuring the time until a short circuit occurs. Specifically, for example, a test for applying a bias voltage at a temperature of 85 ° C. and a humidity of 85% RH, called HHBT (High temperature and Highness Bias Test) or THB (HemptyStress High) For example, a test in which a bias voltage is applied at a temperature of 130 ° C. and a humidity of 85% RH.

<Electronic parts>
An aspect of the present invention also includes an electronic component that is sealed and insulated with the moisture-proof insulating paint of the present invention. Examples of the electronic component include a microcomputer, a transistor, a capacitor, a resistor, a relay, a transformer, and a mounting circuit board on which these are mounted, and also includes a lead wire, a harness, a film substrate, and the like that are joined to these electronic components. be able to.

  Moreover, the signal input part of flat panel display panels, such as a liquid crystal display panel, a plasma display panel, an organic electroluminescent panel, a field emission display panel, the touch sensor of a touch panel, its wiring, etc. are mentioned as an electronic component.

  The electronic component of the present invention can be produced by applying the moisture-proof insulating paint of the present invention to an electronic component and then curing the applied moisture-proof insulating paint. As a specific method for producing the electronic component of the present invention, first, the above-described moisture-proof insulating coating is applied to the electronic component by a generally known method such as dipping, brushing, spraying, or drawing. . Next, an electronic component is obtained by irradiating ultraviolet rays using a high-pressure mercury lamp, a metal halide lamp, an LED or the like as a light source and curing the coating film of the moisture-proof insulating coating applied to the electronic component.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not restrict | limited only to a following example.

(Synthesis Example 1)
In a reaction vessel equipped with a stirrer and a water separator, 22.00 g of Sovermol (registered trademark) 908 (hydrogenated dimer diol manufactured by BASF, hydrogenated dimer diol purity 97.5 wt%), EMPOL (registered trademark) 1008 (hydrogenated by BASF) Dimer acid, hydrogenated dimer acid purity 92.0%) 23.00g, Neostan U-810 (dioctyltin dilaurate manufactured by Nitto Kasei Co., Ltd.) 0.01g, about 240 ° C, starting from normal pressure, condensing water flowing out The mixture was then subjected to dehydration esterification while reducing pressure, and a mixture of a polyester polyol and a hydrogenated dimer diol having a hydroxyl value of 59 mg KOH / g, a number average molecular weight of 2000 and containing 15% by mass of a hydrogenated dimer diol (hereinafter referred to as polyester polyol A and I wrote.)

(Synthesis Example 2)
In a 300 mL reaction vessel equipped with a stirrer, a thermometer, and a condenser, 45.00 g of polyester polyol A, Sovermol (registered trademark) 908 (hydrogenated dimer diol manufactured by BASF, purity of hydrogenated dimer diol 97.5 wt%) .94 g, 0.82 g of Nonion (registered trademark) L-2 (polyethylene glycol monolaurate manufactured by NOF Corporation), Irganox (registered trademark) 1010 (pentaerythritol tetrakis [3- (3,5-di-tert) manufactured by BASF -Butyl-4-hydroxyphenyl)] propionate) 0.12 g, Neostan U-810 (dioctyltin dilaurate manufactured by Nitto Kasei Co., Ltd.) and VESTANAT (registered trademark) H12MDI (methylenebis (4- by Evonik Degussa) Cyclohe The sill isocyanate)) was charged 32.62G, with stirring, the temperature was raised to 75-80 ° C. using an oil bath. Thereafter, the reaction was continued with stirring for 2.5 hours. Thereafter, 20.69 g of 4-HBA (4-hydroxybutyl acrylate, manufactured by Osaka Organic Chemical Industry Co., Ltd.) was charged into the reaction vessel, and the temperature in the reaction vessel was kept within the range of 80 ° C. ± 5 ° C. while continuing stirring. The reaction was continued for 10 hours. Thereafter, an infrared absorption spectrum was measured, and it was confirmed that the absorption of the isocyanate group had disappeared. The reaction was terminated, and urethane acrylate (hereinafter referred to as urethane acrylate B) was obtained.

(Synthesis Example 3)
In a 300 mL reaction vessel equipped with a stirrer, a thermometer and a condenser, 34.0 g of Sovermol (registered trademark) 908 (hydrogenated dimer diol manufactured by BASF, hydrogenated dimer diol purity 97.5 wt%) and 100 mg of hydroquinone monomethyl ether were added. While stirring, the temperature was raised to 40 ° C. using an oil bath. Thereafter, methylenebis (4-cyclohexylisocyanate) (manufactured by Evonik Degussa, trade name: VESTANAT (registered trademark) H12MDI) 32.60 g (124.2 mmol) and Neostan U-810 (Nitto Kasei Co., Ltd. dioctyltin dilaurate) was 0. 0.01 g was added, and the temperature was raised to an internal temperature of 90 ° C while stirring was continued. After raising the temperature to 90 ° C., the reaction was continued with stirring for 4 hours. Thereafter, 17.91 g (124.2 mmol) of 4-hydroxybutyl acrylate was charged into the reaction vessel, and the reaction was continued for 6 hours while maintaining the temperature in the reaction vessel in the range of 90 ° C. ± 5 ° C. while continuing stirring. Continued. Thereafter, the infrared absorption spectrum was measured, and it was confirmed that the absorption of the isocyanato group had disappeared. The reaction was terminated, and urethane acrylate (hereinafter referred to as urethane acrylate C) was obtained.

(Synthesis Example 4)
After introducing air gas into a reaction vessel equipped with a stirrer, thermometer, cooling pipe and air gas introduction pipe, HEA (2-hydroxyethyl acrylate manufactured by Osaka Organic Chemical Industry Co., Ltd.) 53.00 g, GI-1000 ( Charge 600.00 g of hydrogenated polybutadiene diol manufactured by Nippon Soda Co., Ltd. (number average molecular weight: about 1,500) and 0.50 g of hydroquinone monomethyl ether (manufactured by Wako Pure Chemical Industries, Ltd.), and use an oil bath at 70 ° C. The temperature was raised to. Then, it heat-retained for 30 minutes at 70-75 degreeC, stirring, and 70.00 g of Coronate (trademark) T-65 (Nippon Polyurethane Industry Co., Ltd. tolylene diisocyanate) was uniformly dripped at this in 3 hours. After completion of the dropwise addition, the reaction was continued at 70 to 75 ° C. with stirring for about 5 hours. Thereafter, an infrared absorption spectrum was measured, and it was confirmed that absorption of the isocyanato group had disappeared. The reaction was terminated, and urethane acrylate (hereinafter referred to as urethane acrylate D) was obtained.

(Synthesis Example 5)
In a 1-liter four-necked flask equipped with a stirrer and a distillation apparatus, 540.0 g of hydrogenated polybutadiene polyol (manufactured by Nippon Soda Co., Ltd., trade name: NISSO-PB GI-2000, hydroxyl value 47.3 mgKOH / g), acrylic 162.0 g of n-butyl acid, 0.81 g of dioctyltin dilaurate and pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (trade name: IRGANOX 1010 manufactured by BASF Corporation) ) 3.51 g was added and heated to 130 ° C. in an air stream, and the mixture of n-butanol and n-butyl acrylate was gradually refluxed over about 10 hours while refluxing. Distilled off. After n-butanol and n-butyl acrylate disappeared, the pressure in the reaction system was reduced to 10 kPa using a vacuum pump, and n-butanol and n-butyl acrylate were again distilled out of the system. After maintaining at 50 Pa for about 1.5 hours, the reactor was cooled to obtain hydrogenated polybutadiene diacrylate (hereinafter referred to as polyol polyacrylate E).

Example 1
4.50 g of urethane acrylate B, 4.50 g of IBXA (Isobornyl acrylate manufactured by Osaka Organic Chemical Industry Co., Ltd.), 0.80 g of Blemmer LA (lauryl acrylate manufactured by NOF Corporation), A-DPH (Shin Nakamura) 0.20 g of dipentaerythritol hexaacrylate manufactured by Chemical Industry Co., Ltd. and 1.00 g of Karenz MT (registered trademark) PE1 (pentaerythritol tetrakis (3-mercaptobutyrate) manufactured by Showa Denko KK) as a mercapto group-containing compound, TR-PBG-304 as a photopolymerization initiator 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole- manufactured by CHANGZHOU TRONLY NEW ELECTRONIC MATERIALS CO., LTD. 3-Ile 0.10 g of 3-cyclopentylpropanone-1- (O-acetyloxime), Irgacure (registered trademark) 369 (2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 manufactured by BASF ) Is mixed with 0.10 g of DISPALON L-1982N (acrylic copolymer manufactured by Enomoto Kasei Co., Ltd.) as an antifoaming agent using Narataro ARE-310 (rotary / revolving mixer manufactured by Sinky Co., Ltd.) This blend was designated as moisture-proof insulating paint B1.

(Examples 2-9, Comparative Examples 1-2)
By the method similar to Example 1, it mix | blended with the component and quantity as shown in Table 1, and obtained moisture-proof insulating coating B2-B6, C1, D1, E1, F1, G1.

  In Table 1, Irgacure (registered trademark) 651 is benzyl dimethyl ketal manufactured by BASF, Karenz MT (registered trademark) BD1 is 1,4-bis (3-mercaptobutyryloxy) butane manufactured by Showa Denko KK, Karenz MT (registered trademark) NR1 is 1,3,5-tris (3-mercaptobutyryloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione manufactured by Showa Denko KK EBECRYL3700 is a bisphenol A type epoxy resin acrylic acid adduct.

<Evaluation of deep curability>
Deep part curability was evaluated by the following method.
Apply moisture-proof insulating paints B1 to B6, C1, D1, E1, F1, and G1 on a polyimide film (trade name: Kapton (registered trademark) 150EN, manufactured by Toray DuPont Co., Ltd.) to a thickness of 1 mm. A moisture-proof insulating coating applied by irradiating ultraviolet rays under the conditions of an illuminance of 400 mW / cm 2 and an exposure amount of 300 mJ / cm 2 using an ultraviolet irradiation device (made by Eye Graphics) using an LED-UV lamp (wavelength 365 nm) The case where the thickness of the cured portion after wiping off the uncured liquid portion was 700 μm or more was designated as A, the case where the thickness was 500 μm or more was designated as B, and the case where the thickness was less than 500 μm was designated as C. The results are shown in Table 1.

<Evaluation of surface curability>
The surface curability was evaluated by the following method.
Apply moisture-proof insulating paints B1 to B6, C1, D1, E1, F1, and G1 on a polyimide film (trade name: Kapton (registered trademark) 150EN, manufactured by Toray DuPont Co., Ltd.) to a thickness of 500 μm. The surface of the moisture-proof insulating coating is irradiated with ultraviolet rays under the conditions of an illuminance of 400 mW / cm 2 and an exposure amount of 300 mJ / cm 2 using an ultraviolet irradiation device (made by Eye Graphics Co., Ltd.) using an LED-UV lamp (wavelength 365 nm). When the paper was pressed on and peeled off after 2 seconds, the case where no penetration of uncured paint was found on the surface of the dust-free paper that touched the moisture-proof insulating paint was observed. A, but the surface of the moisture-proof insulating paint was not wet. The case was designated as B, and the case where the surface of the moisture-proof insulating paint was wet was designated as C. The results are shown in Table 1.

<Evaluation of long-term electrical insulation reliability using flexible substrates>
A substrate having a fine comb pattern shape described in JPCA-ET01, manufactured by etching a flexible copper-clad laminate (manufactured by Sumitomo Metal Mining Co., Ltd., grade name: Esperflex, copper thickness: 8 μm, polyimide thickness: 38 μm) Copper wiring width / copper wiring width = 15 μm / 15 μm) Tin-plated flexible wiring board with moisture-proof insulating paints B1 to B6, C1, D1, E1, F1, and G1, each having a cured thickness of 150 μm Then, using an ultraviolet irradiation device (made by Eye Graphics Co., Ltd.) using an LED lamp (wavelength 365 nm), it was cured by irradiation with ultraviolet rays under the condition of an irradiation amount of 300 mJ / cm 2.

  Using this test piece, a bias voltage of 30 V was applied, and a temperature and humidity steady test under conditions of a temperature of 85 ° C. and a humidity of 85% RH was performed using MIGRATION TESTER MODEL MIG-8600 (manufactured by IMV). Table 1 shows resistance values 1000 hours after the start of the temperature and humidity steady test.

  It can be seen from Table 1 that the moisture-proof insulating coatings B1 to 4, C1, D1, E1, F1, and G1 containing the mercapto group-containing compound have both high depth curability and surface curability. It can be seen that the moisture-proof insulating coatings B5 to B6 that do not contain a mercapto group-containing compound are inferior in deep-part curability or surface curability. That is, it was found that the moisture-proof insulating paint of the present invention has both high deep part curability and surface curability as compared with a moisture-proof insulating paint that does not contain a mercapto group-containing compound.

The moisture-proof insulating paint of the present invention has both high deep part curability and surface curability. Further, the sealing treatment / insulation treatment performed using the moisture-proof insulating paint and the LED-UV lamp of the present invention has a low environmental load and is low in cost. An electronic component sealed and insulated using the moisture-proof insulating paint of the present invention has high reliability and is useful for a mounted circuit board on which a microcomputer and various components are mounted.

Claims (11)

A moisture-proof insulating paint comprising a (meth) acryloyl group-containing compound (1), a photopolymerization initiator (2), and a mercapto group-containing compound (3). The photopolymerization initiator (2) has the formula (1)

(In the formula, R ¹ is a hydrocarbon group which may contain a hetero atom, and R ² and R ³ are hydrocarbon groups.)
The moisture-proof insulating paint according to claim 1, which is a compound represented by the formula: and / or benzyldimethyl ketal. The moisture-proof insulating paint according to claim 1 or 2, wherein the mercapto group-containing compound (3) has two or more mercapto groups per molecule. The moisture-proof insulating paint according to any one of claims 1 to 3, wherein the mercapto group-containing compound (3) has a secondary mercapto group.   The (meth) acryloyl group-containing compound (1) contains at least one selected from the group consisting of polyol poly (meth) acrylate, epoxy (meth) acrylate, urethane (meth) acrylate, and (meth) acrylic monomer. The moisture-proof insulating paint according to any one of 1 to 4.   The (meth) acryloyl group-containing compound (1) includes at least one selected from the group consisting of polyol poly (meth) acrylate, epoxy (meth) acrylate and (meth) acrylic monomer, and urethane (meth) acrylate, The moisture-proof insulating paint according to any one of claims 1 to 5.   7. The urethane (meth) acrylate comprises a structure derived from a polyester polyol having a structural unit derived from a hydrogenated dimer acid and a structural unit derived from a hydrogenated dimer diol. The moisture-proof insulating paint described.   Furthermore, the moisture-proof insulation coating material of any one of Claims 1-7 containing (4) silane coupling agents.   Furthermore, the moisture-proof insulation coating material of any one of Claims 1-8 containing (5) tackifier.   The sealing insulation processing method of an electronic component including the process of apply | coating the moisture-proof insulating coating material of any one of Claims 1-9 to an electronic component, irradiating an application part with an LED-UV lamp, and making it harden | cure. An electronic component that has been sealed and treated with the moisture-proof insulating paint according to claim 1.